Fischer carbene complexes of cobalt(I) : synthesis and structure |
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Author: | Moeng, Mmushi M.1; Malan, Frederick P.1; Lotz, Simon1; |
Organizations: |
1Department of Chemistry, University of Pretoria, Private Bag X20, Hatfield 0028, Pretoria, South Africa 2Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland |
Format: | article |
Version: | published version |
Access: | open |
Online Access: | PDF Full Text (PDF, 1.3 MB) |
Persistent link: | http://urn.fi/urn:nbn:fi-fe202201051214 |
Language: | English |
Published: |
Elsevier,
2022
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Publish Date: | 2022-01-05 |
Description: |
AbstractThree different aryl substrates thiophene (ThH), ferrocene (FcH) and p-bromodimethylaniline (p-DMABr) were lithiated and reacted with [Co(CO)₄SnPh₃], according to the Fischer carbene protocol. The products [CoSnPh₃(CO)₃{C(OEt)R}] (R =Th, 1, p-DMA, 2 and R = Fc, 3) were analysed to unravel the role of the aryl carbene substituent in stabilizing intermediates and final products. The ethoxy carbene complexes were aminolysed by in situ generated HNMe₂ to afford [CoSnPh₃(CO)₃{C(NMe₂)R}] (R =Th, 4, p-DMA, 5) and with N,N-dimethylethylenediamine [CoSnPh₃(CO)₃{C(NHCH₂CH₂NMe₂)R}] (R = p-DMA, 6) in high yields. The trigonal Co(CO)₃ in the equatorial plane is very stable and efforts to displace a carbonyl in 6 was unsuccessful, both by heating and irradiation. The role of the aryl carbene substituents in stabilizing the electrophilic carbene carbon was investigated and studied by NMR spectroscopy in solution and single crystal X-ray structure determinations. see all
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Series: |
Journal of molecular structure |
ISSN: | 0022-2860 |
ISSN-E: | 1872-8014 |
ISSN-L: | 0022-2860 |
Volume: | 1252 |
Article number: | 132093 |
DOI: | 10.1016/j.molstruc.2021.132093 |
OADOI: | https://oadoi.org/10.1016/j.molstruc.2021.132093 |
Type of Publication: |
A1 Journal article – refereed |
Field of Science: |
116 Chemical sciences |
Subjects: | |
Funding: |
The authors gratefully acknowledge the National Research Foundation, South Africa [NRF 105740; NRF 105529 NRF 87788 and NRF 9772] and Sasol Technology R&D Pty. Ltd. (South Africa) for financial support. |
Copyright information: |
© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) . |
https://creativecommons.org/licenses/by/4.0/ |